TWI418572B - Polycarbonate resin and manufacturing method thereof - Google Patents

Abstract

The present invention can provide a polycarbonate resin containing a structural unit represented by the following formula (1). In the formula (1), R represents one selected from an alkyl group having 1 to 9 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an aralkyl group having 7 to 17 carbon atoms, and halogen; and n represents the number of substituting R's on a benzene ring and is an integer of 0 to 4. Y represents an alkylene group having 1 to 4 carbon atoms; and p is an integer of 0 to 4.

Description

Polycarbonate resin and method of producing the same

The present invention relates to a novel polycarbonate resin. The preferred embodiment of the invention relates to a transparency, heat resistance, high refractive index, low photoelastic coefficient, low birefringence and high mechanical strength. A novel polycarbonate resin and an optical material using the same. The polycarbonate resin of the present invention can be suitably used as a plastic optical product such as various optical lenses, iridium, optical disk substrates, optical fibers, optical communication devices, or optical materials used for optical films.

In recent years, with the advancement of photovoltaics, there has been an increasing demand for optically transparent polymers which are optically excellent isotropic. In particular, an optical film having optical characteristics suitable for a retardation film of a liquid crystal display or the like is expected.

A polycarbonate resin, especially a polycarbonate film, obtained by reacting 2,2-bis(4-hydroxyphenyl)propane (generally referred to as bisphenol A) with phosgene or a carbonic acid diester can be used for packaging purposes, optics. In various industrial applications such as devices and display devices, recently, in photovoltaic devices such as liquid crystal display devices, materials such as phase difference plates, polarizing plates, and plastic substrates have been attracting attention, and their practical use has progressed. In particular, in the liquid crystal display device, in the TFT type liquid crystal display device which is improved in the past, the phase difference film used between the liquid crystal layer and the polarizing plate for improving the visibility of the image has been attracting attention.

The retardation film serves to convert the elliptically polarized light that has passed through the liquid crystal layer into a linearly polarized light. Then, the material can be mainly composed of bisphenol A. A uniaxially stretched film of polycarbonate resin.

However, when considering a retardation film, in the film obtained by molding a polycarbonate resin composed of bisphenol A, the photoelastic coefficient is large due to the optical anisotropy of the benzene ring of the polycarbonate resin. Therefore, the variation of the phase difference due to the low stretch ratio may become large. Further, the film used for the liquid crystal display requires a high temperature treatment of 180 ° C or higher in the alignment film forming process or the like, and there is a problem that the heat resistance is insufficient.

In the case of a polycarbonate resin having a high heat resistance and a low photoelastic coefficient, a polycarbonate resin having a specific ruthenium structure has been proposed (for example, refer to Japanese Laid-Open Patent Publication No. Hei 6-25398 (Patent Document 1), JP-A-2001 -253960 (Patent Document 2)).

However, the polycarbonate resin having such a structure is high in heat resistance and low in photoelasticity, but the film is broken when stretched or taken up, and is not resistant to bending, and the bending strength is weak when the film is curled. At this time, a smooth cut surface cannot be obtained, and it is feared that cracking occurs during stretching, and the film strength is insufficient, and improvement is desired.

Moreover, since the conventional aromatic polycarbonate resin is a material having high photoelasticity and low fluidity, there is a problem that birefringence is large due to molecular alignment or residual stress during molding. Therefore, when forming an optical material consisting of a conventional aromatic polycarbonate resin, in order to improve fluidity, a resin having a relatively low molecular weight is used, and a method of reducing birefringence of a product by high-temperature molding is performed. However, in the conventional aromatic polycarbonate resin, even if the above-mentioned means are used, the reduction of birefringence is still limited, so in recent years, with optical The development of materials has led to the development of materials with low photoelastic coefficients and high fluidity in a part of the field of optical materials. Therefore, development of a resin having low birefringence has been carried out.

In addition, since the refractive index of the optical material is high, that is, the lens element can be realized with a smaller curvature surface, the amount of aberration generated on the surface can be reduced, and the number of lenses can be reduced, the eccentricity of the lens can be reduced, and the lens thickness can be reduced. The reduction is made thereby making the lens system compact and lightweight. Further, in the spectacle lens, the lens of the same degree can be thinned, so that the appearance is excellent.

In the case of an optical resin having a high refractive index and a low birefringence, a wholly aromatic polycarbonate resin copolymer of a bisphenol having a fluorene structure having a large polarizability in the side chain direction has been studied (for example, refer to Japanese Patent Laid-Open) Japanese Patent Publication No. 6-25398 (Patent Document 1).

Further, a homopolycarbonate resin having an oxime structure having a large polarizability in the side chain direction and having an ether diol having a phenol skeleton in a linear direction, or a copolymer thereof with a bisphenol ( Japanese Patent Publication No. Hei 10-101787 (Patent Document 4) and JP-A-10-101786 (Patent Document 5)).

Further, there is a proposal for a copolymer of a bisphenol having a high polarizability and a tricyclodecane [5.2.1.0 ^2,6 ] dimethanol in the side chain direction (refer to Japanese Laid-Open Patent Publication No. 2000-169573 ( Patent Document 6)).

Although there have been developments of various low birefringence materials as described above, there are problems in such techniques that the refractive index is low or the moldability is insufficient, and a satisfactory molded article or coloring cannot be obtained. point.

Further, although the monomer bismuth bisphenol is a conventional one, it can be used only as a photoresist composition, but the resin having the skeleton and its characteristics are completely unknown, and the resin is not used for a specific use. Japanese Laid-Open Patent Publication No. 2005-326838 (Patent Document 7) and JP-A-2005-346024 (Patent Document 8)).

[Patent Document 1] JP-A-2001-253960 (Patent Document 3) JP-A-7-109342 (Patent Document 4) Japanese Patent Laid-Open No. 10-101787 [Patent Document 5] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 2005-326838. Bulletin No. -346024

The present invention has at least one of the above-mentioned problems to be solved in view of such circumstances, and in particular, to provide transparency, high refractive index, heat resistance, low birefringence, and low light which are applicable to optical materials. A novel polycarbonate resin having a high modulus of elasticity and high mechanical strength, a method for producing the polycarbonate resin, and an optical material using the polycarbonate resin.

In order to solve the above problems, the inventors of the present invention have found that a polycarbonate resin containing a structural unit represented by the following formula (1) can be found. The invention is completed by at least one of transparency, high refractive index, heat resistance, low birefringence, low photoelastic coefficient, and high mechanical strength.

That is, the above problems can be solved by the following invention.

<1> An embodiment of the present invention is a polycarbonate resin containing a structural unit represented by the following formula (1).

(In the formula (1), R represents an alkyl group selected from a carbon number of 1 to 9, an aryl group having 6 to 12 carbon atoms, an olefin group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a carbon number. a aralkyl group of 7 to 17 and a halogen; n represents the number of substitutions of R on the benzene ring, an integer of 0 to 4; Y represents an alkylene group having 1 to 4 carbon atoms; p is 0 to 4 Integer)

(2) The polycarbonate resin according to the above <1>, further comprising a structural unit represented by the following formula (2): (In the formula (2), R represents an alkyl group selected from a carbon number of 1 to 9, an aryl group having 6 to 12 carbon atoms, an olefin group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a carbon number. a aralkyl group of 7 to 17 and a halogen; m represents the number of substitutions of R on the benzene ring, and is an integer from 0 to 4; X represents: Wherein R ₁ and R ₂ represent hydrogen, fluorine, chlorine, bromine, iodine, an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, and a carbon number of 2; An alkene group of 5 or an aralkyl group having 7 to 17 carbon atoms; further, R ₁ and R ₂ may be bonded to form a carbocyclic or heterocyclic ring; and R ₃ and R ₄ respectively represent hydrogen, fluorine, chlorine, bromine, iodine, An alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or an aryl group having 6 to 12 carbon atoms; R _{5 being} an alkylene group having 1 to 9 carbon atoms; a representing an integer of 0 to 20, b Represents an integer from 1 to 500)

(3) The polycarbonate resin according to the above <1>, further comprising a structural unit represented by the following formula (3): (In the formula (3), Y is an alkylene group or a cycloalkylene group having a carbon number of 0 to 20 or a structure represented by the following formula (4))

(In the formula (4), R ₁ , R ₂ , R ₃ and R ₄ are each a hydrogen atom or an alkyl group having 1 to 5 carbon atoms)

(4) The polycarbonate resin according to the above <3>, wherein the structural unit represented by the above formula (1) is 5 to 90 mol% of the total structural unit.

<5> The polycarbonate resin according to the above <3> or <4>, wherein the structural unit represented by the above formula (3) is a tricyclic ring [5.2.1.0 ^{2, 6} ]decane dimethanol, 1,4-cyclohexanedimethanol, or 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2, 4, 8, 10-tetraoxa Residue of spiro(5.5) undecane.

<6> The polycarbonate resin according to the above <1> or <2>, wherein the glass transition temperature is 150 ° C or more and the photoelastic coefficient is 50 × 10 ^-12 m ² / The strength at a time of N or less and a film of 100 μm is 70 MPa or more.

<7> The polycarbonate resin according to the above <3> or <4>, wherein the photoelastic coefficient is 50 × 10 ^-12 m ² /N or less, and the glass transition temperature is 100. The temperature is above 180 ° C and the refractive index nD is 1.57 or more.

<8> A preferred embodiment of the invention is the polycarbonate resin according to any one of the above items <1> to <7>.

In a preferred embodiment of the present invention, there is provided an optical lens comprising the polycarbonate resin according to any one of the items <1> to <7>.

<10> Another preferred aspect of the present invention is an optical film comprising The polycarbonate resin according to any one of the above items <1> to <7>.

In a preferred embodiment of the invention, the method for producing a polycarbonate resin according to the above <2>, which is characterized in that the dihydroxy compound represented by the following formula (5) is used and The dihydroxy compound shown in (6) is reacted with a compound forming a carbonate in the presence of a polymerization catalyst. (In the formula (5), R represents an alkyl group selected from carbon atoms 1 to 9, an aryl group having 6 to 12 carbon atoms, an olefin group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a carbon number. a aralkyl group of 7 to 17 and a halogen; n represents the number of substitutions of R on the benzene ring, an integer of 0 to 4; X represents an alkylene group having 1 to 4 carbon atoms; and p is 0 to 4 Integer)

(In the formula (6), R represents an alkyl group selected from carbon atoms 1 to 9, an aryl group having 6 to 12 carbon atoms, an olefin group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a carbon number. a aralkyl group of 7 to 17 and a halogen; m represents the number of substitutions of R on the benzene ring, an integer from 0 to 4; X represents: Wherein R ₁ and R ₂ represent hydrogen, fluorine, chlorine, bromine, iodine, an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, and a carbon number of 2; An alkene group of 5 or an aralkyl group having 7 to 17 carbon atoms; further, R ₁ and R ₂ may be bonded to form a carbocyclic or heterocyclic ring; and R ₃ and R ₄ respectively represent hydrogen, fluorine, chlorine, bromine, iodine, An alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or an aryl group having 6 to 12 carbon atoms; R _{5 being} an alkylene group having 1 to 9 carbon atoms; a representing an integer of 0 to 20, b Represents an integer from 1 to 500).

In a preferred embodiment of the invention, the method for producing a polycarbonate resin according to the above <3>, which is characterized in that the dihydroxy compound represented by the following formula (5) is used and 7) The dihydroxy compound shown reacts with a carbonic acid diester in the presence of a polymerization catalyst, (In the formula (5), R represents an alkyl group selected from carbon atoms 1 to 9, an aryl group having 6 to 12 carbon atoms, an olefin group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a carbon number. a aralkyl group of 7 to 17 and a halogen; n represents the number of substitutions of R on the benzene ring, an integer of 0 to 4; X represents an alkylene group having 1 to 4 carbon atoms; and p is 0 to 4 Integer)

HOCH ₂ -Y-CH ₂ OH (7) (In the formula (7), Y is an alkylene group or a cycloalkylene group having a carbon number of 0 to 20 or a structure represented by the following formula (4))

(In the formula (4), R ₁ , R ₂ , R ₃ and R ₄ are each a hydrogen atom or an alkyl group having 1 to 5 carbon atoms)

By using the polycarbonate resin of the preferred aspect of the present invention, various optical lenses, iridium, optical disk substrates, and optical fibers having transparency, heat resistance, high refractive index, low photoelastic coefficient, and low birefringence can be produced. Optical materials such as plastic optical products or optical films.

Hereinafter, the polycarbonate resin of the present invention and a method for producing the same will be specifically described.

Polycarbonate resin

The polycarbonate resin of the present invention is characterized by containing a structural unit represented by the following formula (1).

In addition to the structural unit represented by the following formula (1), it is preferable to contain a structural unit represented by the following formula (2).

It contains a structural unit represented by the following formula (1) (hereinafter, also referred to as "structural In the copolymer of the unit (1) and the structural unit represented by the following formula (2) (hereinafter also referred to as "structural unit (2)", the ratio (mol%) of the structural unit (1) is [ In the case of the structural unit (1) / the structural unit (1) + the structural unit (2), it is preferably 5 mol% or more. When the ratio of the structural unit (1) is 5 mol% or more, the heat resistance is improved, so that it is preferable. In the copolymer, the ratio of the structural unit (1) is from 10 to 85 mol%, which is particularly preferable because of a good balance between optical properties and moldability.

(In the formula (1), R represents an alkyl group selected from a carbon number of 1 to 9, an aryl group having 6 to 12 carbon atoms, an olefin group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a carbon number. a aralkyl group of 7 to 17 and a halogen; n represents the number of substitutions of R on the benzene ring, an integer of 0 to 4; Y represents an alkylene group having 1 to 4 carbon atoms; p is 0 to 4 Integer).

In the formula (1), R is preferably an alkyl group selected from the group consisting of C 1 to 4, an aryl group having 6 to 12 carbon atoms, an olefin group having 2 to 4 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, One of the aralkyl groups having a carbon number of 7 to 13 and a halogen is more preferably a methyl group, a cyclohexyl group or a phenyl group.

n is preferably an integer from 0 to 1. Preferably, Y is an alkylene group having 1 to 2 carbon atoms, and p is an integer of 0 to 1.

Specific examples of such a structural unit (1) include, for example, 1,1-bis(4-hydroxyphenyl)fluorene, or 1,1-bis(4-cresol) anthracene, or 1,1-bis(phenoxy). Ethanol) Residues such as 苊. These may contain two or more types, and are particularly preferably 1,1-bis(4-hydroxyphenyl)anthracene.

Next, a structural unit represented by the following formula (2) will be described.

In the formula (2), R represents an alkyl group selected from carbon atoms 1 to 9, an aryl group having 6 to 12 carbon atoms, an olefin group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a carbon number. 7 to 17 aralkyl and halogen; m represents the number of substitutions of R on the phenyl ring, an integer from 0 to 4; X represents: R ₁ and R ₂ represent hydrogen, fluorine, chlorine, bromine, iodine, an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, and a carbon number of 2 to 2, respectively. An alkene group of 5 or an aralkyl group having 7 to 17 carbon atoms. Further, R ₁ and R ₂ may be bonded to form a carbocyclic or heterocyclic ring.

R ₃ and R ₄ each represent an alkyl group having a carbon number of hydrogen, fluoro, chloro, bromo, iodo, 1 to 9 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or an aryl group of 6 to 12; R ₅ based carbon number An alkylene group of 1 to 9; a represents an integer of 0 to 20, and b represents an integer of 1 to 500.

In the formula (2), R is preferably an alkyl group selected from the group consisting of a C 1 to 4 carbon number, an aryl group having 6 to 12 carbon atoms, an olefin group having 2 to 4 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, A kind of aralkyl group having a carbon number of 7 to 13 and a halogen. More preferably, R is a methyl group, a cyclohexyl group, or a phenyl group. Preferred examples of X include isopropylidene groups, methylene groups, and anthranilyl groups.

When the polycarbonate resin containing the structural unit (1) or the polycarbonate resin containing the structural units (1) and (2) is used as a film or a sheet, in order to obtain sufficient strength, the intrinsic viscosity (also referred to as the ultimate viscosity) is preferable. It is preferably from 0.30 to 2.0 dl/g, more preferably from 0.40 to 1.5 dl/g. Further, the intrinsic viscosity is a viscosity increase rate per unit concentration of a polymer obtained in a thin solution which can be ignored in the influence of contact between polymers.

The glass transition temperature of the polycarbonate resin containing the structural unit (1) or the polycarbonate resin containing the structural units (1) and (2) is preferably 120 ° C or higher, more preferably 120 to 180 ° C. If the glass transition temperature is from 120 to 180 ° C, it is easy to form and shape.

The photoelastic coefficient of the polycarbonate resin containing the structural unit (1) or the polycarbonate resin containing the structural units (1) and (2) is preferably 50 × 10 ^-12 m ² /N or less, more preferably 30 × 10 ^-12 m ² /N. When the photoelastic coefficient is 50 × 10 ^-12 m ² /N or less, it is difficult to produce birefringence.

The polycarbonate resin containing the structural unit (1) or the polycarbonate resin containing the structural units (1) and (2) preferably has a strength of 70 MPa or more, more preferably 80 to 100 MPa, as a film of 100 μm. When the strength is 70 MPa or more, the film strength is improved.

Average molecular weight (Mw) of polycarbonate resin containing structural unit (1) It is preferably 25,000 to 55,000, more preferably 30,000 to 45,000. Further, the average molecular weight (Mw) of the polycarbonate resin containing the structural units (1) and (2) is preferably from 25,000 to 55,000, more preferably from 30,000 to 45,000.

Further, even in the range in which the effects of the present invention are not impaired, it is possible to contain a carbonate unit other than the structural unit (1) and the structural unit (2).

In addition, the polycarbonate resin of the present invention preferably contains a structural unit represented by the following formula (3) in addition to the structural unit represented by the following formula (1) (hereinafter, also referred to as "structural unit (3) Copolymer.

In the formula, Y is an alkylene group or a cycloalkylene group having a carbon number of 0 to 20 or a structure represented by the following formula (4).

In the formula (4), R ₁ , R ₂ , R ₃ and R ₄ are each a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

Specific examples of such a structural unit (3) include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,4-cyclohexanedimethanol. And a linear diol of 1,6-hexanediol; tricyclo[5.2.1.0 ^2,6 ]decane dimethanol, 4, 10-dimethyltricyclo[5.2.1.0 ^2,6 ]decane dimethanol , 4, 4, 10, 10-tetramethyltricyclo[5.2.1.0 ^2,6 ]decane dimethanol, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10-decamethyl Tricyclo[5.2.1.0 ^2,6 ]decane dimethanol, 3,9-bis(2-hydroxyethyl)-2, 4,8-tetraoxaspiro(5.5)undecane, 3, 9-bis(2-hydroxy-1,1-diethylethyl)-2, 4, 8, 10-tetraoxaspiro(5.5)undecane, 3,9-bis(2-hydroxy-1 , 1-dipropylethyl)-2, 4, 8, 10-tetraoxaspiro(5.5) undecane, 1,4-cyclohexanediol (trans, cis or mixtures thereof a residue of a cyclic diol. These dihydroxy compounds can be used in one type or in combination of two or more types.

Among these, it is particularly preferred to be selected from the group consisting of tricyclo [5.2.1.0 ^2,6 ]decane dimethanol, 1,4-cyclohexanedimethanol, and 3,9-bis(2-hydroxy-1, 1-di Residue of the dihydroxy compound of methylethyl)-2,4,8,10-tetraoxaspiro(5.5)undecane.

The polycarbonate resin containing the structural units (1) and (3) is a copolymer of a structural unit represented by the above formula (1) and a structural unit represented by the formula (3) in a random, block, or interactive bond. The average molecular weight (Mw) is from 20,000 to 200,000, more preferably from 30,000 to 100,000.

Further, it is possible to contain a carbonate unit other than the structural unit (1) and the structural unit (3) without departing from the effects of the present invention.

In the copolymer containing the structural unit represented by the formula (1) ("structural unit (1)") and the structural unit represented by the formula (3) ("structural unit (3)"), the structural unit (1) The ratio (mol%) is preferably from 5 to 90 mol% in terms of [structural unit (1) / structural unit (1) + structural unit (3)]. When the ratio of the structural unit (1) is 5 mol% or more, the heat resistance is improved. When the ratio of the structural unit (1) is from 10 to 85 mol%, it is more preferable because the balance between optical properties and moldability is good.

The polycarbonate resin containing the structural units (1) and (3) can be formed into a wet type Forming, extrusion molding, compression molding, blow molding, injection molding, and the like are formed by a known method. In particular, in order to obtain sufficient strength by injection molding, the inherent viscosity (limit viscosity) of the polycarbonate resin is preferably from 0.30 to 2.0 dl/g, more preferably from 0.40 to 1.5 dl/g. If the intrinsic viscosity is 0.30 dl/g or more, sufficient strength can be obtained. When the intrinsic viscosity is 2.0 dl/g or less, the melt viscosity is not excessively high, and the fluidity is good and the molding is easy.

The glass transition temperature of the polycarbonate resin containing the structural units (1) and (3) is preferably 100 ° C or more and 180 ° C or less, more preferably 105 ° C or more and 165 ° C or less. When the glass transition temperature is 100 ° C or more, heat resistance is improved, and it can be used for various purposes. Moreover, when the glass transition temperature is 180 ° C or less, the fluidity is good and the molding process is easy, which is preferable. Further, in order to secure fluidity, it is suppressed at a low molecular weight because it is brittle.

The photoelastic coefficient of the polycarbonate resin containing the structural units (1) and (3) is preferably 50 × 10 ^-12 m ² /N or less, more preferably 30 × 10 ^-12 m ² /N. When the photoelastic coefficient is 50 × 10 ^-12 m ² /N or less, it is difficult to produce birefringence.

The refractive index nD of the polycarbonate resin containing the structural units (1) and (3) is preferably 1.57 or more, and more preferably 1.60 or more. When the refractive index nD is 1.57 or more, the lens can be made thinner.

2. Method for producing polycarbonate resin

A method for producing a polycarbonate resin (homopolymer) containing the structural unit (1) by a step of reacting a bisphenol (dihydroxy compound) represented by the following formula (5) with a carbonate-forming compound The method to manufacture.

Further, the polycarbonate resin containing the structural units (1) and (2) may contain a bisphenol (dihydroxy compound) represented by the following formula (5), and The bisphenol (dihydroxy compound) represented by the formula (6) is produced by a method of reacting a carbonate-forming compound.

Specifically, it is a known method which can be used for producing a polycarbonate resin from a bisphenol A and a carbonate-forming compound, for example, a direct reaction of a bisphenol with phosgene (phosgene method), or a bisphenol and a diaryl group. It is produced by a method such as transesterification of a carbonate (transesterification method).

In the formula (5), R represents an alkyl group selected from a carbon number of 1 to 9, an aryl group having 6 to 12 carbon atoms, an olefin group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a carbon number. 7 to 17 of one of aralkyl and halogen, n represents the number of substitutions of R on the benzene ring, an integer of 0 to 4, X represents an alkylene group having 1 to 4 carbon atoms, and p is 0 to 4 Integer).

In the formula (5), R is preferably an alkyl group selected from the group consisting of a carbon number of 1 to 4, an aryl group having 6 to 12 carbon atoms, an olefin group having 2 to 4 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, One of the aralkyl groups having a carbon number of 7 to 13 and a halogen is more preferably a methyl group, a cyclohexyl group or a phenyl group.

n is preferably an integer from 0 to 1. Preferably, X is an alkylene group having 1 to 2 carbon atoms, and p is an integer of 0 to 1.

Here, the bisphenol represented by the above formula (5) may, for example, be 1,1-bis(4-hydroxyphenyl)fluorene or 1,1-bis(4-cresol)pyrene, or 1,1. a residue of bis(phenoxyethanol)hydrazine or the like. These systems can also use more than 2 types, especially 1, 1- Bis(4-hydroxyphenyl)indole.

Next, the dihydroxy compound represented by the following formula (6) will be described.

In the formula (6), R represents an alkyl group selected from a carbon number of 1 to 9, an aryl group having 6 to 12 carbon atoms, an olefin group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a carbon number of 7 To one of 17 aralkyl groups and halogens, m represents the number of substitutions of R on the phenyl ring, an integer from 0 to 4, and X represents: R ₁ and R ₂ represent hydrogen, fluorine, chlorine, bromine, iodine, an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, and a carbon number of 2 to 2, respectively. An alkene group of 5 or an aralkyl group having 7 to 17 carbon atoms; further, R ₁ and R ₂ may be bonded to form a carbocyclic or heterocyclic ring.

R ₃ and R ₄ each represent an alkyl group having a carbon number of hydrogen, fluoro, chloro, bromo, iodo, 1 to 9 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or an aryl group of 6 to 12; R ₅ based carbon number An alkylene group of 1 to 9; a represents an integer of 0 to 20, and b represents an integer of 1 to 500.

In the formula (6), preferred R represents an alkyl group selected from a carbon number of 1 to 4 and a carbon number. An aryl group of 6 to 12, an alkene group having 2 to 4 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, an aralkyl group having 7 to 13 carbon atoms, and a halogen. More preferably, R is a methyl group, a cyclohexyl group or a phenyl group.

Here, the bisphenol represented by the above formula (6) is various, and specific examples thereof include the following compounds. 1,1'-biphenyl-4,4'-diol, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, bis(4-hydroxybenzene) Ether, bis(4-hydroxyphenyl)arylene, bis(4-hydroxyphenyl) sulfide, bis(4-hydroxyphenyl)anthracene, bis(4-hydroxyphenyl)one, 2, 2- Bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-t-butylphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1, 1-bis(4-hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, double ( 4-hydroxyphenyl)diphenylmethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 9,9-bis(4-hydroxyphenyl)anthracene, 9,9-double (4-hydroxy-3-methylphenyl)indole, α,ω-bis[2-(p-hydroxyphenyl)ethyl]polydimethyloxane, α,ω-double [3-(o -hydroxyphenyl)propyl]polydimethyloxane, 4,4'-[1,3-phenylenebis(1-methylethylidene)]bisphenol, 1, 1-double (4 -Hydroxyphenyl)-1-phenylethane and the like. These systems can also be used in combination of two or more types. Further, among these, it is particularly preferably selected from the group consisting of 2,2-bis(4-hydroxyphenyl)propane (bisphenol A: BPA) and 2, 2-bis(4-hydroxy-3-methylphenyl). Propane (bisphenol C: BPC), bis(4-hydroxyphenyl)ether, 1,1-bis(4-hydroxyphenyl)cyclohexane (bisphenol Z:BPZ), and 1,1-bis(4- Hydroxyphenyl)-1-phenylethane (bisphenol AP: BPAP), etc., more preferably BPA or BPZ.

Further, the carbonate-forming compound may, for example, be phosgene or diphenyl carbonate, di-p-tolyl carbonate or phenyl-p-tolyl carbonate. Diaryl carbonate such as di-p-chlorophenyl carbonate or dinaphthyl carbonate. These compounds may be used in combination of two or more types.

In the phosgene method, the bisphenol represented by the formula (5) is reacted with phosgene in the presence of an acid binder and a solvent, or the bisphenol represented by the formula (5) and the formula (6) are used. The bisphenol shown reacts with phosgene. As the acid binder, for example, pyridine or a hydroxide of an alkali metal such as sodium hydroxide or potassium hydroxide can be used, and for the solvent, for example, dichloromethane, chloroform or the like can be used. Further, in order to promote the polycondensation reaction, a catalyst such as a tertiary amine or a fourth-order ammonium salt such as triethylamine is preferably added, and in the polymerization degree adjustment, phenol, p-tert-butylphenol, p-cumene is preferably added. A monofunctional compound such as a phenol, a long-chain alkyl-substituted phenol, or an olefin-substituted phenol is used as a molecular weight modifier. Further, as desired, a small amount of an antioxidant such as sodium sulfite or dithionite or a branching agent such as phloroglucin or ruthenium bisphenol may be added. The appropriate reaction is generally from 0 to 150 ° C, preferably in the range of from 5 to 40 ° C. The reaction time is affected by the reaction temperature, but it is usually from 0.5 minute to 10 hours, preferably from 1 minute to 2 hours. Further, in the reaction, it is preferred to maintain the pH of the reaction system at 10 or more.

Further, in the transesterification method, a bisphenol represented by the formula (5) is mixed with a bisaryl carbonate, or a bisphenol represented by the formula (5) and a bisphenol represented by the formula (6) are used. The bisaryl carbonate is mixed and reacted under reduced pressure at a high temperature. The reaction is generally carried out at a temperature in the range of from 150 ° C to 350 ° C, preferably in the range of from 200 to 300 ° C, and the degree of reduced pressure is preferably less than 1 mm Hg at the end, such that the bisaryl carbonate derived from the transesterification process is derived. The phenols are distilled off the system. Although the reaction time is affected by the reaction temperature, the degree of pressure reduction, etc., it is usually about 1 to 4 hours. The reaction is preferably carried out under an inert gas atmosphere such as nitrogen or argon. Again, on demand The reaction may also be carried out by adding a molecular weight regulator, an antioxidant, or a branching agent. The additives relating to these are as follows.

The method for producing the film or the sheet may be any method, but is preferably a solution casting method (casting method). The solvent used for the solution casting method may be any solvent which can dissolve the polycarbonate copolymer, and is preferably dichloromethane, tetrahydrofuran, dioxane or the like.

Further, the polycarbonate resin containing the structural units (1) and (3) is obtained by including a dihydroxy compound represented by the following formula (5) and a dihydroxy compound represented by the following formula (7) in a polymerization catalyst. In the presence of a reaction with a compound forming a carbonate, it is produced.

The relevant formula (5) is as described above.

Next, the dihydroxy compound represented by the formula (7) will be explained.

HOCH ₂ -Y-CH ₂ OH (7)

In the formula, Y is an alkylene group or a cycloalkylene group having a carbon number of 0 to 20 or a structure represented by the following formula (4).

In the formula (4), R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom or a monovalent alkyl group having 1 to 5 carbon atoms.

The dihydroxy compound represented by the formula (7) may specifically be, for example, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol or 1,4-cyclohexane. Linear diol of dimethanol and 1,6-hexanediol, tricyclo[5.2.1.0 ^2,6 ]decane dimethanol, 4, 10-dimethyltricyclo[5.2.1.0 ^2,6 ]癸Alkanediethanol, 4, 4, 10, 10-tetramethyltricyclo[5.2.1.0 ^2,6 ]decane dimethanol, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10- Decamethyltricyclo[5.2.1.0 ^2,6 ]decane dimethanol, 3,9-bis(2-hydroxyethyl)-2, 4,8 10-tetraoxaspiro(5.5)undecane ,3,9-bis(2-hydroxy-1,1-diethylethyl)-2, 4, 8, 10-tetraoxaspiro(5.5)undecane, 3,9-bis(2- Hydroxy-1,1-dipropylethyl)-2, 4, 8, 10-tetraoxaspiro(5.5) undecane, 1,4-cyclohexanediol (trans, cis isomer) Or a mixture thereof) a cyclic dihydroxy compound. These dihydroxy compounds may be used in combination of two or more types.

Among these, it is particularly preferred to be selected from the group consisting of tricyclo [5.2.1.0 ^2,6 ]decane dimethanol, 1,4-cyclohexanedimethanol, and 3,9-bis(2-hydroxy-1, 1-di Residue of the dihydroxy compound of methylethyl)-2,4,8,10-tetraoxaspiro(5.5)undecane.

Further, examples of the carbonate-forming compound include phosgene, diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, di-p-chlorophenyl carbonate, and the like. A bisaryl carbonate such as dinaphthyl carbonate. These compounds may be used in combination of two or more types.

Further, in the transesterification method, a dihydroxy compound represented by the formula (5) and a dihydroxy compound represented by the formula (7) are mixed with a bisaryl carbonate, and the mixture is reacted under reduced pressure at a high temperature. The reaction is generally carried out at a temperature in the range of from 150 ° C to 350 ° C, preferably in the range of from 200 to 300 ° C, and the degree of reduced pressure is preferably 1 mm Hg at the end. Hereinafter, the phenols derived from the bisaryl carbonate formed by the transesterification reaction are distilled off to the outside of the system. The reaction time is affected by the reaction temperature, the degree of pressure reduction, etc., but is usually about 1 to 4 hours. The reaction is preferably carried out under an inert gas atmosphere such as nitrogen or argon. Further, a reaction may be carried out by adding a molecular weight modifier, an antioxidant or a branching agent as needed.

In the present invention, in addition to the specific compound described above, the aromatic-aliphatic polycarbonate resin copolymer may be simultaneously added with various known additives depending on the purpose without departing from the physical properties.

Examples of the antioxidant include triphenylphosphite, tris(4-methylphenyl)phosphite, tris(4-t-butylphenyl)phosphite, and tris(monodecylphenyl)phosphoric acid. Ester, tris(2-methyl-4-ethylphenyl) phosphite, tris(2-methyl-4-tributylphenyl)phosphite, tris(2,4-di-third) Phenyl)phosphite, tris(2,6-di-t-butylphenyl)phosphite, tris(2,4-di-t-butyl-5-methylphenyl)phosphite, three (mono, dimercaptophenyl) phosphite, bis(monodecylphenyl)pentaerythritol-di-phosphite, bis(2,4-di-t-butylphenyl)pentaerythritol-di-phosphite , bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol-di-phosphite, bis(2,4,6-tri-t-butylphenyl)pentaerythritol-di-phosphite Ester, bis(2,4-di-t-butyl-5-methylphenyl)pentaerythritol-di-phosphite, 2,2-methylenebis(4,6-dimethylphenyl)octyl Phosphite, 2,2-methylenebis(4-tert-butyl-6-methylphenyl)octylphosphite, 2,2-methylenebis(4,6-di-third Butylphenyl)octyl phosphite, 2,2-methylenebis(4,6-dimethylphenyl) Phosphite, 2,2-methylenebis(4,6-di-t-butylphenyl)hexylphosphite, 2,2-methylenebis(4,6-di-t-butylbenzene) Stearylphosphoric acid a phosphite compound such as an ester; pentaerythritol-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-( 3, 5-di-t-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 1, 3, 5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, triethylene glycol-bis[3-(3- Tributyl-5-methyl-4-hydroxyphenyl)propionate], 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl) Propyloxy]-1,1-dimethylethyl}-2, 4, 8, 10-tetraoxaspiro[5,5]undecane, 1, 1, 3-tris[2- A hindered phenolic compound such as 4-(3,5-di-tert-butyl-4-hydroxyphenylpropenyloxy)-5-t-butylphenyl]butane; 5, 7-di Tributyl-3-(3,4-dimethylphenyl)-3H-benzofuran-2-one and the like. These may be used alone or in combination of two or more.

The antioxidant is added in an amount of usually 0.005 to 0.1% by weight, preferably 0.01 to 0.08% by weight, more preferably 0.01 to 0.05% by weight based on 100% by weight of the aromatic-aliphatic polycarbonate resin copolymer. If the amount is less than this, the desired effect cannot be obtained, and when it is excessive, the heat resistant physical properties and mechanical properties are lowered.

The ultraviolet absorber may, for example, be 2-(5-methyl-2-hydroxyphenyl)benzotriazole or 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)benzene. -2H-benzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-tert-butyl-5-methyl-2 -hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di-tert-butyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3, 5-di Third amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-th-octylphenyl)benzotriazole, 2,2'-methylene double [4 -(1, 1, 3, 3-tetramethyl Butyl)-6-[(2H-benzotriazol-2-yl)phenol]], 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5- [(hexyl)oxy]-phenol, 2, 4-dihydroxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxyl Benzophenone and the like. These may be used alone or in combination of two or more.

The release agent may be a general user, and examples thereof include natural, synthetic paraffin, polyoxyxylene oil, polyethylene wax, beeswax, stearic acid, hard acid monoglyceride, stearic acid stearyl ester, Fatty acid esters such as palmitic acid monoglyceride, behenic acid behenate, lauric acid monoglyceride, pentaerythritol distearate, pentaerythritol tetrastearate, etc., which may be used alone or in combination 2 More than one species.

Other flame retardants, antistatic agents, pigments, dyes, polymer modifiers, slip agents, plasticizers, and the like may be used singly or in combination as needed.

The present invention provides an optical material obtained by using the above polycarbonate resin of the present invention.

The above-mentioned optical material may be exemplified by various optical lenses, optical disks, optical disks, optical communication devices, and the like, and optical optical products or optical films. When the polycarbonate resin of the present invention is supplied to the above-mentioned use, it can be used as a dye, a refractive index adjuster, an inorganic fine particle or the like to which a known antioxidant, ultraviolet absorber, light stabilizer, fluorescent dye or photochromic dye is added. The PC resin composition is used.

[Examples]

The invention is illustrated by the following examples, but the invention is not limited by the examples. Further, the measured values in the examples were measured by the following methods or apparatuses.

1) Intrinsic viscosity (limit viscosity): Ubbelohde viscosity tube is used. The solution was measured at 20 ° C, 0.5% dichloromethane, with a Huggins constant of 0.45.

2) Glass transition temperature (Tg) and differential thermal scanning calorimeter (DSC) were used for measurement.

3) Photoelastic coefficient: By using an elliptical polarizer (Ellipsometer), a cast film having a thickness of 100 μm was used to irradiate light having a laser wavelength of 633 nm, and was calculated from a birefringence measurement of a change in load.

4) Film strength and elongation: The tensile strength and tensile longation of the film having a thickness of 100 μm obtained in the examples were determined according to ASTM D882-61T using Shimadzu Autograph AGS-100G manufactured by Shimadzu Corporation. .

5) Light transmission rate: measured by Model 1001DP manufactured by Nippon Denshoku Industries Co., Ltd.

6) Refractive index: Polycarbonate was press-formed into a rectangular parallelepiped of 3 mm thick × 8 mm × 8 mm, and measured by a refractometer manufactured by ATAGO Co., Ltd.

7) Birefringence: Measured by an ellipsometer made by a Japanese spectrophotometer.

<Synthesis Example 1>

10308g, acetic acid 3250ml, cobalt(II) hexahydrate and 30.6g, cobalt (II) acetate tetrahydrate and 6.1g, manganese (II) acetate tetrahydrate and 1.5 in a 10-liter three-necked flask. g, after stirring and mixing to dissolve all, the air was poured into the solution at 400 ° C/hr under normal pressure at 20 ° C. The reaction was stopped after 4.3 hours, and the reaction product was analyzed by gas chromatography. As a result, a enthalpy conversion rate of 99.2% and an indole-1-one yield of 28.1% were obtained.

(Synthesis Example 2)

To 1 kg of the reaction product obtained in Synthesis Example 1, 1 liter of toluene and 2 liters of water were added, and the mixture was stirred for 5 minutes and extracted, and then allowed to stand for 15 to 20 minutes to carry out liquid separation, and the upper layer of toluene was collected. The above extract and the same amount of 4% aqueous sodium hydroxide solution were placed in a separatory funnel, and the mixture was shaken and allowed to stand to remove the black liquid of the lower layer. The residual liquid is added and washed with the same amount of water to remove the lower layer. Further, water was added and 2 ml of hydrochloric acid was added to vibrate, and the lower layer liquid was removed, followed by washing with water. Further, the oil layer was subjected to alkali washing, and then concentrated to remove the solvent. The concentrate was distilled at a pressure of 1 to 2 mmHg, and 16 g of indole-1-one was distilled off at a distillation temperature of 120 °C.

(Synthesis Example 3)

Into a 500 ml three-necked flask, 10 g of indole-1-one obtained in Synthesis Example 2, 195 g of phenol, 0.8 g of 98% sulfuric acid, and 0.6 g of thioacetic acid were fed, and the mixture was stirred at 50 ° C for 30 hours under a nitrogen atmosphere to be cooled. After the temperature was reached, the resulting liquid, 200 ml of toluene and 60 ml of a 2% aqueous sodium hydroxide solution were placed in a separatory funnel, and the mixture was shaken and allowed to stand, and the aqueous layer was removed. The oil layer was concentrated with a rotary evaporator, further reduced to 1 to 2 mmHg, and the phenol was distilled off at 90 °C. To 20 g of the obtained solid matter, 200 g of toluene was added, and the mixture was heated to reflux with toluene and dissolved, and then left to cool to room temperature. The precipitated crystals were collected by filtration, washed in the order of toluene and water, and then dried.

The results of elemental analysis of the obtained crystals were C 85.19%, H 5.36%, and O 9.45% (calculated values: C 85.18%, H 5.35%, O 9.46%). As a result of GC-MS analysis, the molecular weight of 1,2-bis(4-hydroxyphenyl)fluorene of the object was 338. The chemical shift values (δ ppm, TMS basis) of ¹ H-NMR in acetone-d ₆ solvent were 4.09 (s, 2H), 6.72 (q, 4H), 7.05 (q, 4H), 7.18 (d, 1H). ), 7.36 (d, 1H), 7.51 (q, 2H), 7.68 (q, 2H), 8.22 (s, 2H). Further, the FT-IR was measured by the KBr tablet method, and the characteristic absorption band such as a functional group or a bond was a hydroxyl group (3308 cm ^-1 , 1242 cm ^-1 ) benzene ring (1595 cm ^-1 , 1507 cm ^-1 , 1432 cm ^{-1 ).} , 787 cm ^-1 ), naphthalene ring (1595 cm ^-1 , 1507 cm ^-1 , 1432 cm ^-1 , 1176 cm ^-1 , 787 cm ^-1 ). The purity of 19.2 g of the obtained crystal was 96.9% after GC analysis.

[Example 1]

1,1-bis(4-hydroxyphenyl)anthracene (hereinafter abbreviated as "ANBP") obtained in Synthesis Example 3, 203.0 g (0.6 mol) and Liana, were obtained in 1100 ml of a 5 w/w% aqueous sodium hydroxide solution. Sulfate 0.1g. Further, 500 ml of dichloromethane was added and stirred while maintaining at 15 ° C, and then 90 g of phosgene was blown in over 90 minutes. After the phosgene blowing was completed, 4.18 g of tert-butylphenol (hereinafter referred to as "PTBP": manufactured by Dainippon Ink and Chemicals Co., Ltd.) was added as a molecular weight modifier, and the reaction liquid was emulsified by vigorous stirring. After emulsification, 0.6 was added. The triethylamine of ml was polymerized by stirring at about 20 to 25 ° C for about 1 hour.

After the completion of the polymerization, the reaction liquid is separated into an aqueous phase and an organic phase, and the organic phase is neutralized with phosphoric acid, and washed with water until the conductivity of the washing liquid (aqueous phase) becomes 10 μS/cm or less. The obtained polymer solution was dropped on warm water maintained at 45 ° C, and the solvent was evaporated to give a white powdery precipitate. The obtained precipitate was filtered and dried at 105 ° C for 24 hours to obtain a polymer powder.

The solution having a concentration of dichloromethane of the polymer of 0.5 g/dl as a solvent had an ultimate viscosity of 0.60 dl/g at 20 °C. The absorbent polymer obtained by the infrared spectroscopic analysis, the results can be seen in position in the vicinity of 1170cm ^-1 by the absorption of a carbonyl group and the position in the vicinity of 1240cm ^-1 absorption by an ether bond, comprising shown confirmed by the following formula (1) of The polycarbonate resin of the structural unit. The structural formula of the obtained resin is as follows.

The obtained resin was dissolved in dichloromethane (polymer solution concentration: 20% by weight) and cast to prepare a film.

(Example 2)

The same procedure as in Example 1 was carried out except that ANBP 101.5 g (0.3 mol) and 2.2-bis(4-hydroxyphenyl)propane (bisphenol A:BPA) 68.4 g (0.3 mol) were used. The structural formula of the obtained resin is as follows.

(Comparative Example 1)

Upilon E-2000 (manufactured by Mitsubishi Engineering Plastics Co., Ltd.) was used as the polycarbonate resin composed of bisphenol A. The structural formula of this resin is as follows.

(Comparative Example 2)

The same procedure as in Example 1 was carried out except that 9,9-bis(4-hydroxyphenyl)fluorene 175.2 g (0.5 mol) was used. The structural formula of the obtained resin As follows.

(Comparative Example 3)

The same procedure as in Example 1 was carried out except that 9,9-bis(4-hydroxyphenyl)fluorene 105.1 g (0.3 mol) and BPA 68.4 (0.3 mol) were used. The structural formula of the obtained resin is as follows.

The physical properties of the resins and films obtained in Examples 1 to 2 and Comparative Examples 1 to 3 were measured, and the results are shown in Table 1 below. The polycarbonate resin of the present invention is a resin containing a monomer having an anthracene skeleton. As is apparent from the results of Table 1, it is understood that the present invention provides a polycarbonate resin which has excellent strength, permeability, and low photoelastic coefficient, and which is suitable for use in a phase difference film application.

(Example 3)

1,1-bis(4-hydroxyphenyl)indole (ANBP) obtained in the above Synthesis Example 3, 9.313 kg (25.275 mol), tricyclo[5.2.1.0 ^2,6 ]undecane dimethanol (below) Abbreviated as TCDDM) 8.448kg (43.04 moles), diphenyl carbonate (hereinafter referred to as DPC) 15.00kg (70.01 moles), and sodium bicarbonate 0.000574g (6.8μmol) were placed in a mixer and distillation In a 50 liter reactor other than the apparatus, the nitrogen atmosphere was heated to 215 ° C for 1 hour under 760 mmHg, and stirred.

Thereafter, the pressure reduction was adjusted to 150 mmHg over 15 minutes, and the mixture was maintained at 215 ° C and 150 mmHg for 20 minutes to carry out a transesterification reaction. Further, the temperature was raised to 240 ° C at a rate of 37.5 ° C / hr, and maintained at 240 ° C and 150 mmHg for 10 minutes. Thereafter, it was adjusted to 120 mmHg for 10 minutes, maintained at 240 ° C, 120 mmHg for 70 minutes, and then, for 10 minutes. The temperature was adjusted to 100 mmHg, maintained at 240 ° C and 100 mmHg for 10 minutes, further adjusted to 1 mmHg or less for 40 minutes, and stirred under the conditions for 10 minutes. After the completion of the reaction, nitrogen gas was poured into the reactor and pressurized, and the produced polycarbonate resin was removed while being granulated. The polycarbonate resin obtained had an ultimate viscosity of 0.66 and a Tg of 128 °C. The structural formula of the obtained resin is as follows.

10.0 kg of this polycarbonate resin was vacuum-dried at 100 ° C for 24 hours, and an antioxidant such as ADK STAB PEP36 (trade name: manufactured by Asahi Kasei Kogyo Co., Ltd.) 500 ppm, and an antioxidant HP 136 (trade name: Ciba specialty Chemicals) was added to the resin. 200 ppm of glycerol monostearate and 300 ppm of glyceryl monostearate were prepared by kneading at 250 ° C under an extruder to obtain granules. The particle has an ultimate viscosity of 0.64. The pellet was vacuum dried at 100 ° C for 24 hours, and then injection-molded at a cylinder temperature of 250 ° C and a mold temperature of 120 ° C to obtain a lenticular lens having a convex radius of 9.4 mm and a convex radius of 5.0 mm. Further, after measuring the optical characteristics of the obtained resin lens, it was confirmed that the refractive index was 1.576, the photoelastic coefficient was 11 × 10 ^-12 m ² /N, and the birefringence was 15 nm, and the birefringence was extremely small and substantially optically deformed. lens. Further, the total light transmittance measured was 89%.

(Example 4)

The same procedure as in Example 1 was carried out except that 8.269 kg (22.44 mol) of ANBP, 7.552 kg (52.36 mol) of cyclohexanedimethanol (cis-trans mixture), and 16.423 kg (76.68 mol) of DPC were used. The structural formula of the obtained resin is as follows.

After measuring the optical characteristics of the obtained resin lens, it was confirmed that the refractive index was 1.585, the photoelastic coefficient was 17 × 10 ^-12 m ² /N, and the birefringence was 20 nm, and the birefringence was extremely small, and the lens was not substantially optically deformed. Further, the total light transmittance measured was 89%.

(Example 5)

Except for the use of ANBP 14.348 kg (38.94 mol), 2, 4, 8, 10-tetraoxaspiro(5.5) undecane 8.941 g (29.37 mol), and diphenyl carbonate DPC 15.00 kg (70.01 mol) The rest is the same as in the first embodiment. The structural formula of the obtained resin is as follows.

After measuring the optical characteristics of the obtained resin lens, it was confirmed that the refractive index was 1.575, the photoelastic coefficient was 25 × 10 ^-12 m ² /N, and the birefringence was 23 nm, and the birefringence was extremely small, and the lens was not substantially optically deformed. Further, the total light transmittance was measured to be 89%.

(Comparative Example 4)

Upilon H-4000 (manufactured by Sangai Engineering Plastics Co., Ltd.) was used as the polycarbonate resin composed of bisphenol A. The structural formula of this resin is as follows.

The pellet was vacuum dried at 100 ° C for 24 hours, and then injection-molded at a cylinder temperature of 255 ° C and a mold temperature of 120 ° C to obtain a lenticular lens having a convex radius of 5.0 mm and a convex radius of 5.0 mm. Further, after measuring the optical characteristics of the obtained resin lens, it was confirmed that the refractive index was 1.584, the photoelastic coefficient was 78 × 10 ^-12 m ² /N, the birefringence was 230 nm, and the birefringence was large and the optical distortion was large. . Further, the total light transmittance measured was 89%.

(Comparative Example 5)

Zeonex 330R (manufactured by Zeon Corporation, Japan) was used. The structural formula of this resin is as follows.

The pellet was vacuum dried at 100 ° C for 24 hours, and then injection-molded at a cylinder temperature of 260 ° C and a mold temperature of 120 ° C to obtain a lenticular lens having a convex radius of 9.4 mm and a convex radius of 5.0 mm. After measuring the optical characteristics of the obtained resin lens, it was confirmed that the refractive index was 1.530, the photoelastic coefficient was 3.2×10 ^-12 m ² /N, and the birefringence was 45 nm, and the birefringence was extremely small and there was no optical distortion. The rate is 1.53. Further, the total light transmittance measured was 90%.

The physical properties of the resins and lenses obtained in Examples 3 to 5 and Comparative Examples 4 to 5 were measured, and the results are shown in Table 2 below.

From the results of Table 2, it is understood that according to the present invention, a novel polycarbonate resin having transparency, heat resistance, high refractive index, low photoelastic coefficient, and low birefringence can be obtained.

(industrial availability)

The polycarbonate resin of the present invention can be suitably used as a plastic optical product and an optical film of various lenses, enamels, optical disk substrates, optical fibers, and the like.

Claims (12)

A polycarbonate resin containing a structural unit represented by the following formula (1): (In the formula (1), R represents an alkyl group selected from a carbon number of 1 to 9, an aryl group having 6 to 12 carbon atoms, an olefin group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a carbon number. a aralkyl group of 7 to 17 and a halogen; n represents the number of substitutions of R on the benzene ring, an integer of 0 to 4; Y represents an alkylene group having 1 to 4 carbon atoms; p is 0 to 4 Integer). The polycarbonate resin according to claim 1, which further comprises a structural unit represented by the following formula (2): (In the formula (2), R represents an alkyl group selected from a carbon number of 1 to 9, an aryl group having 6 to 12 carbon atoms, an olefin group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a carbon number. a aralkyl group of 7 to 17 and a halogen; m represents the number of substitutions of R on the benzene ring, an integer from 0 to 4; X represents: , -S-, -(CH ₂ )a-, -O-, -SO-, -CO-, -SO ₂ - , or Wherein R ₁ and R ₂ represent hydrogen, fluorine, chlorine, bromine, iodine, an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, and a carbon number of 2; An alkene group of 5 or an aralkyl group having 7 to 17 carbon atoms; further, R ₁ and R ₂ may be bonded to form a carbocyclic or heterocyclic ring; and R ₃ and R ₄ respectively represent hydrogen, fluorine, chlorine, bromine, iodine, An alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or an aryl group having 6 to 12 carbon atoms; R _{5 being} an alkylene group having 1 to 9 carbon atoms; a representing an integer of 0 to 20, b Represents an integer from 1 to 500). The polycarbonate resin according to claim 1, which further comprises a structural unit represented by the following formula (3): (In the formula (3), Y is a chemical bond, an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms or a structure represented by the following formula (4): (In the formula (4), R ₁ , R ₂ , R ₃ and R ₄ are each a hydrogen atom or an alkyl group having 1 to 5 carbon atoms). The polycarbonate resin according to claim 3, wherein the structural unit represented by the above formula (1) is 5 to 90 mol% in the total structural unit. A polycarbonate resin according to claim 3 or 4, wherein the structural unit represented by the above formula (3) is a tricyclo[5.2.1.0 ^2,6 ]decane dimethanol, 1,4-cyclohexane The residue of dimethanol or 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro(5.5)undecane. The polycarbonate resin according to claim 1 or 2, wherein the glass transition temperature is 150 ° C or more, the photoelastic coefficient is 50 × 10 ^-12 m ² /N or less, and the strength as a film of 100 μm is 70 MPa or more. . The polycarbonate resin according to claim 3, wherein the photoelastic coefficient is 50 × 10 ^-12 m ² /N or less, the glass transition temperature is 100 ° C or more and 180 ° C or less, and the refractive index nD is 1.57 or more. An optical material comprising the polycarbonate resin according to any one of claims 1 to 7. An optical lens comprising the polycarbonate resin according to any one of claims 1 to 7. An optical film comprising the polycarbonate resin according to any one of claims 1 to 7. A method for producing a polycarbonate resin according to the second aspect of the patent application, characterized in that the dihydroxy compound represented by the following formula (5) and the following formula are used The dihydroxy compound shown in (6) is reacted with a compound forming a carbonate in the presence of a polymerization catalyst, (In the formula (5), R represents an alkyl group selected from carbon atoms 1 to 9, an aryl group having 6 to 12 carbon atoms, an olefin group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a carbon number. a aralkyl group of 7 to 17 and a halogen; n represents the number of substitutions of R on the benzene ring, an integer of 0 to 4; X represents an alkylene group having 1 to 4 carbon atoms; and p is 0 to 4 Integer) (In the formula (6), R represents an alkyl group selected from carbon atoms 1 to 9, an aryl group having 6 to 12 carbon atoms, an olefin group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a carbon number. a aralkyl group of 7 to 17 and a halogen; m represents the number of substitutions of R on the benzene ring, an integer from 0 to 4; X represents: , -S-, -(CH ₂ )a-, -O-, -SO-, -CO-, -SO ₂ - , or Wherein R ₁ and R ₂ represent hydrogen, fluorine, chlorine, bromine, iodine, an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, and a carbon number of 2; An alkene group of 5 or an aralkyl group having 7 to 17 carbon atoms; further, R ₁ and R ₂ may be bonded to form a carbocyclic or heterocyclic ring; and R ₃ and R ₄ respectively represent hydrogen, fluorine, chlorine, bromine, iodine, An alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or an aryl group having 6 to 12 carbon atoms; R _{5 being} an alkylene group having 1 to 9 carbon atoms; a representing an integer of 0 to 20, b Represents an integer from 1 to 500). A method for producing a polycarbonate resin according to the third aspect of the patent application, wherein the production method is characterized by using a dihydroxy compound represented by the following formula (5) and having the following formula The dihydroxy compound shown in (7) is reacted with a carbonic acid diester in the presence of a polymerization catalyst, (In the formula (5), R represents an alkyl group selected from carbon atoms 1 to 9, an aryl group having 6 to 12 carbon atoms, an olefin group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a carbon number. a aralkyl group of 7 to 17 and a halogen; n represents the number of substitutions of R on the benzene ring, an integer of 0 to 4; X represents an alkylene group having 1 to 4 carbon atoms; and p is 0 to 4 Integer) HOCH ₂ -Y-CH ₂ OH (7) (in the formula (7), a Y-based chemical bond, an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms or a formula (4) ) shown) (In the formula (4), R ₁ , R ₂ , R ₃ and R ₄ are each a hydrogen atom or an alkyl group having 1 to 5 carbon atoms).